JP2003226804A - Polycarbonate resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition having excellent solvent resistance, compatibility (without delamination or defective appearance), high fluidity, flame retardance, sliding properties, weld strength, or the like, and to provide a molded product of the resin composition. <P>SOLUTION: The polycarbonate resin composition comprises (C) 0.05-30 pts.mass of a flame retardant, (D) 0-2 pts.mass of a fluororesin and (E) 0-20 pts.mass of an inorganic filler in 100 pts.mass of resins composed of (A) 60-97 mass% of a polycarbonate resin having molecular terminals blocked with phenoxy groups each having a 10-35C alkyl group and (B) 3-40 mass% of a polyolefinic resin. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polycarbonate resin composition and, more particularly, to a highly compatible, layered resin comprising an aromatic polycarbonate resin, a polyolefin resin, a flame retardant, a fluorine resin and an inorganic filler. The present invention relates to a flame-retardant polycarbonate resin composition having excellent solvent resistance and sliding characteristics without peeling or poor appearance, and a molded product of the resin composition.

[0002]

2. Description of the Related Art Polycarbonate resins are engineering plastics having excellent transparency and impact resistance, but have the drawback that they are highly hygroscopic and are easily attacked by organic solvents and the like. In order to improve such disadvantages, an invention relating to a blend of a polycarbonate resin and a polyolefin resin has been proposed. For example, Japanese Patent Publication No. 40-1
Japanese Patent Publication No. 3663 discloses a blend of a polycarbonate resin and a polyethylene resin, and Japanese Patent Publication No. 40-13664 discloses a blend of a polycarbonate resin and a polypropylene resin. However, since these two resins have low compatibility with each other, delamination occurs with a simple blend, and the molding appearance is poor, so that they have not been put to practical use.

[0003] In order to improve the compatibility of these two components, attempts have been made to coexist with a compatibilizer.
For example, JP-A-59-223742 discloses a method using a modified polypropylene resin and JP-A-3-2690.
No. 34 proposes a method using a modified polypropylene resin and an oxazoline group-containing resin. JP 6
JP-A-3-215750 discloses a method of using an epoxy-modified polypropylene-based resin and a polycarbonate-based resin having a terminal carboxyl group when blending a bisphenol A-type polycarbonate-based resin and a polypropylene-based resin, and JP-A-6-220262 discloses a polycarbonate-based resin. When blending with polyolefin resin,
A method using a carboxylic acid-modified polycarbonate resin and an epoxy-modified polyolefin resin has been proposed.
However, by imparting a functional group such as carboxylic acid to the terminal of the polycarbonate resin, the compatibility is improved, but conversely, the thermal stability is reduced, which causes a reduction in the molecular weight and coloring of the polycarbonate resin during molding. There is. Japanese Patent Laid-Open No. 7-10216 discloses a technique of adding an inorganic filler to a polycarbonate resin and a polyolefin resin.
Although it is disclosed in JP-A-5, it does not describe compatibilization.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a solvent-resistant,
An object of the present invention is to provide a flame-retardant polycarbonate resin composition having excellent compatibility (no delamination or poor appearance), high fluidity, slidability, weld strength, and the like, and a molded article of the resin composition. Is what you do.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has selected a specific polycarbonate-based resin and used a polyolefin-based resin, a flame retardant, a fluorine-based resin and an inorganic filler. The present inventors have found that a resin composition comprising the combination is excellent in solvent resistance, sliding properties and flame retardancy without delamination or poor appearance, and completed the present invention.

That is, the present invention provides: (A) 60 to 97% by mass of a polycarbonate resin whose molecular terminal is sealed with a phenoxy group having an alkyl group having 10 to 35 carbon atoms and (B) a polyolefin resin 3 to
(C) with respect to 100 parts by mass of the resin composed of 40% by mass.
0.05 to 30 parts by mass of flame retardant, (D) fluororesin 0
1. a polycarbonate resin composition containing 2 parts by mass and (E) 0 to 20 parts by mass of an inorganic filler; The above-mentioned 1., wherein the polyolefin-based resin is at least one resin selected from a polyethylene-based resin and a polypropylene-based resin. 2. The polycarbonate resin composition according to the above, (1) The flame retardant is one or more flame retardants selected from phosphorus flame retardants, organic alkali metal salts, organic alkaline earth metal salts, and silicone flame retardants. 3. The polycarbonate resin composition according to the above, The above-mentioned 1., wherein the fluororesin is polytetrafluoroethylene having a fibril-forming ability. 4. The polycarbonate resin composition according to the above, The above-mentioned 1., wherein the inorganic filler is a plate-like filler. 5. The polycarbonate resin composition according to the above, 4. The platy filler is at least one platy filler selected from talc, mica and wollastonite. 6. The polycarbonate resin composition according to the above, The above 1. ~ 6. 7. A molded article comprising the polycarbonate resin composition according to any one of the above, and The above 1. ~ 6. A housing or part of an electric / electronic device comprising the polycarbonate resin composition according to any one of the above. It is about.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polycarbonate resin composition of the present invention comprises (A) 60 to 97% by mass of a polycarbonate resin whose molecular terminal is sealed with a phenoxy group having an alkyl group having 10 to 35 carbon atoms.
And (B) 100 to 100 parts by mass of a resin composed of 3 to 40% by mass of a polyolefin-based resin, and
30 parts by mass, (D) 0 to 2 parts by mass of a fluororesin, and (D) 0 to 20 parts by mass of an inorganic filler.

[0008] The polycarbonate resin composition of the present invention,
As the polycarbonate resin as the component (A), a polycarbonate resin including a polycarbonate resin having a molecular terminal capped with a phenoxy group having an alkyl group having 10 to 35 carbon atoms (abbreviated as “terminal alkylphenoxy modification”). It is characterized by using a resin.

Here, the terminal alkylphenoxy-modified polycarbonate resin can be obtained by using an alkylphenol having an alkyl group having 10 to 35 carbon atoms as a terminal stopper in the production of the polycarbonate resin. The alkylphenol having 10 to 35 carbon atoms is not particularly limited, and decylphenol,
Examples include undecylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol, octadecylphenol, nonadecylphenol, eicosylphenol, and the like.

The alkyl group of these alkylphenols having 10 to 35 carbon atoms has an o-, m-,
It may be at any position of p-, but the position of p- is preferred. The alkyl group may be linear, branched, or a mixture thereof. As this substituent, at least one may be the above-mentioned alkyl group having 10 to 35 carbon atoms, and the other four are not particularly limited, and may be an alkyl group having 1 to 9 carbon atoms, or an aryl group having 6 to 20 carbon atoms. It may be a group, a halogen atom or unsubstituted.

The specific terminal-modified polycarbonate resin may be any of the polycarbonate resins described below. For example, in order to control the molecular weight in the reaction of a dihydric phenol with phosgene or a carbonate compound, these resins may be used. It is obtained by using an alkylphenol having 10 to 35 carbon atoms as a terminal blocking agent.

For example, it can be obtained by reacting a dihydric phenol with phosgene or a polycarbonate oligomer in a methylene chloride solvent in the presence of a triethylamine catalyst and the alkylphenol having an alkyl group having 10 to 35 carbon atoms. Here, the alkylphenol having an alkyl group having 10 to 35 carbon atoms seals one end or both ends of the polycarbonate resin to modify the end. In this case, the terminal modification is at least 20%, preferably at least 50%, based on all terminals. That is, the other terminal is a hydroxyl group terminal or a terminal blocked with another terminal blocking agent described below.

Here, other terminal blocking agents include:
Phenol, p-tert-butylphenol, p-tert- commonly used in the production of polycarbonate resin
Phenols such as octylphenol and p-cumylphenol. If only these phenols are used, a composition satisfying both the excellent compatibility and flame retardancy of the present invention cannot be obtained.

The component (A) of the polycarbonate resin composition of the present invention contains a terminal alkylphenoxy-modified polycarbonate resin, and this specific terminal-modified polycarbonate resin can be used alone. It is also possible to use it as a mixture with a system resin. The content of the specific terminal-modified polycarbonate resin in this case is not particularly limited, but in order to improve the moldability (melt fluidity), all terminals of the polycarbonate resin as the component (A) are taken into consideration. , Usually 20
It is at least 50 mass%, preferably at least 50 mass%, more preferably at least 70 mass%. This content is based on the ratio of the phenoxy group having an alkyl group having 10 to 35 carbon atoms in the terminal-modified polycarbonate resin, the type of the other terminal, the type of the terminal of the other polycarbonate resin, and the melt fluidity of the target composition. It can be appropriately determined in consideration of such factors.

The polycarbonate resin constituting the component (A) of the polycarbonate resin composition of the present invention is not particularly limited, and various resins can be used. Usually, an aromatic polycarbonate produced by reacting a dihydric phenol with a carbonate precursor can be used.
That is, a product produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol with phosgene, or a transesterification method of a dihydric phenol with diphenyl carbonate or the like is used. Can be.

As the dihydric phenol, various ones can be mentioned. In particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl)
Cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis ( 4-hydroxyphenyl) ketone and the like.

Particularly preferred dihydric phenols include:
It is based on bis (hydroxyphenyl) alkane, particularly bisphenol A. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.

The polycarbonate resin may have a branched structure. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane and α, α ′, α ″-.
Tris (4-bidroxyphenyl) -1,3,5-triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis (o-cresol) and the like can be mentioned. In order to control the molecular weight, phenol, pt
-Butylphenol, pt-octylphenol, p
-Cumylphenol or the above-mentioned alkylphenol having an alkyl group having 10 to 35 carbon atoms is used.

The polycarbonate resin composition of the present invention comprises:
As this molecular weight regulator, at least the above-mentioned carbon number 10
It is characterized in that it contains a terminal-modified polycarbonate resin obtained by capping the molecular terminal using an alkylphenol having an alkyl group of from 35 to 35.

The polycarbonate resin and the alkyl-phenoxy-terminal-modified polycarbonate resin used in the present invention include a bifunctional carboxylic acid such as terephthalic acid and polymethylenedicarboxylic acid, and an ester precursor such as an ester-forming derivative thereof. It may be a polyester-polycarbonate copolymer obtained by polymerizing a polycarbonate below, or a mixture of various polycarbonate resins.

Further, the polycarbonate-based copolymer and the terminal alkylphenoxy-modified polycarbonate-based copolymer include, in particular, polycarbonate-polyorganosiloxane copolymer (hereinafter referred to as polycarbonate-based resin-PD).
It may be abbreviated as MS copolymer. ) And terminal alkylphenoxy-modified polycarbonate-based resin-PDMS copolymer. The polycarbonate-based resin-PDMS copolymer is composed of a polycarbonate portion and a polyorganosiloxane portion. For example, a polyorganosiloxane having a reactive group at a terminal constituting the polycarbonate oligomer and the polyorganosiloxane portion (polydimethylsiloxane, Polydiethylsiloxane,
Polymethylphenylsiloxane) in a solvent such as methylene chloride, and then add an aqueous sodium hydroxide solution of bisphenol A, and use a catalyst such as triethylamine.
It can be produced by an interfacial polycondensation reaction.
These polycarbonate resin-PDMS copolymer,
For example, JP-A-3-292359 and JP-A-4-2
No. 02465, JP-A-8-81620, JP-A-8-302178 and JP-A-10-7897.

In the polycarbonate resin-PDMS copolymer and the terminal alkylphenoxy-modified polycarbonate resin-PDMS copolymer, the degree of polymerization of the polycarbonate part is 3 to 100, and the degree of polymerization of the polydimethylsiloxane part is about 2 to 500. Is preferably used. The content of polydimethylsiloxane in the polycarbonate resin-PDMS copolymer and the terminal alkylphenoxy-modified polycarbonate resin-PDMS copolymer (including bisphenol A polycarbonate as a by-product) is as follows:
Usually, it is in the range of 0.2 to 30% by mass, preferably 0.3 to 20% by mass. The viscosity average molecular weight of the polycarbonate resin used in the present invention and the terminal alkylphenoxy-modified polycarbonate resin is usually 10,000 to 100,
000, preferably 11,000 to 40,000, particularly preferably 12,000 to 30,000. Here, these viscosity average molecular weights (Mv) are obtained by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, obtaining the intrinsic viscosity [η], and calculating by the following equation. It is.

[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83 The polycarbonate resin composition of the present invention comprises (A)
As a component, a mixed resin of a polycarbonate resin, an alkyl phenoxy-modified polycarbonate resin, a polycarbonate resin-PDMS copolymer, an alkyl phenoxy-modified polycarbonate resin-PDMS copolymer, or the like can also be used. In this case, it is blended so that the content of polydimethylsiloxane in the entire polycarbonate resin in the component (A) is 0.1 to 10% by mass, preferably 0.3 to 5% by mass.

(B) Polyolefin Resin The polyolefin resin as the component (B) of the polycarbonate resin composition of the present invention includes various resins such as polyethylene resin, polypropylene resin and poly-1-butene resin. Polyolefin resins can be mentioned. Here, examples of the polyethylene resin include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, and a copolymer of ethylene and another α-olefin. Further, as the polypropylene resin, including crystalline propylene homopolymer, crystalline propylene-ethylene block and random copolymer, crystalline propylene-ethylene-α-olefin copolymer and these crystalline propylene polymers And mixtures of elastomers. These polyolefin resins can be used alone or as a mixture of two or more. Then, the melt flow rate (M
FR) (230 ° C., 2.16 kg) is preferably 0.1 kg.
1 to 70 g / 10 min, more preferably 0.1 to 5 g
0 g / 10 min. If it is 0.1 g / 10 min or less, molding becomes difficult, and if it is 70 g / 10 min or more, mechanical properties such as impact resistance are significantly reduced.

The polycarbonate resin composition of the present invention improves the compatibility, solvent resistance and slidability of the resin composition by blending a polyolefin resin with the polycarbonate resin. Here, the compounding ratio of the two resins is such that the polycarbonate resin of the component (A) is 60 to 97% by mass, preferably 70 to 95% by mass, more preferably 75 to 90% by mass, and the polyolefin of the component (B) The content of the system resin is 3 to 40% by mass, preferably 5 to 30% by mass, and more preferably 10 to 25% by mass. here,
If the content of the polycarbonate resin (A) is less than 60% by mass, sufficient mechanical properties such as impact resistance cannot be obtained. 9
If it exceeds 7% by mass, the improvement in solvent resistance and fluidity is insufficient. (B) The polyolefin resin of the component is 3
If it is less than mass%, the solvent resistance is insufficient. On the other hand, if it exceeds 40% by mass, surface layer peeling and poor appearance occur.
In this case, (B) the polyolefin resin includes:
Polyethylene resins and polypropylene resins are preferably used.

The polycarbonate resin composition of the present invention comprises a resin 100 (A) containing 60 to 97% by mass of a polycarbonate resin containing an alkyl phenoxy-modified polycarbonate resin and (B) 3 to 40% by mass of a polyolefin resin. (C) 0.05 parts by weight of flame retardant
To 30 parts by mass, (D) 0 to 2 parts by mass of a fluororesin, and (E) 0 to 20 parts by mass of an inorganic filler.

(C) As the flame retardant, phosphorus-based flame retardants, organic alkali metal salts, organic alkaline earth metal salts, silicone-based flame retardants, halogen-based flame retardants, nitrogen-based flame retardants, metal hydroxides, red phosphorus Known materials such as antimony oxide, expandable graphite and the like can be used according to the purpose. Examples of halogen-based flame retardants include tetrabromobisphenol A, halogenated polycarbonate and halogenated polycarbonate (co) polymers and oligomers thereof, (TBA oligomer), decabromodiphenyl ether, (tetrabromobisphenol) epoxy oligomer, halogenated polystyrene, Examples thereof include halogenated polyolefins. Further, as a nitrogen-based flame retardant, melamine, alkyl group or aromatic group substituted melamine, and as a metal hydroxide,
Examples include magnesium hydroxide and aluminum hydroxide. However, although halogenated flame retardants have relatively good flame retardant efficiency, they may generate harmful gases during molding, corrode molds, and emit harmful substances during incineration of molded products, resulting in environmental pollution and safety. In view of the above, a flame retardant containing no halogen is preferable.

The halogen-free phosphorus-based flame retardants include halogen-free organic phosphorus-based flame retardants. As the organic phosphorus-based flame retardant, any organic compound having a phosphorus atom and containing no halogen can be used without particular limitation. Among them, a phosphate compound having at least one ester oxygen atom directly bonded to a phosphorus atom is preferably used. Examples of the halogen-free phosphorus-based flame retardant other than the organic phosphorus-based compound include red phosphorus.

The phosphate compound is not particularly limited, and preferably does not contain halogen. For example, the following formula (1)

[0030]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, X represents a divalent or higher valent organic group, and p represents 0 or 1; And q represents an integer of 1 or more, and r represents an integer of 0 or more.). In the formula (1), the organic group is an alkyl group which may or may not be substituted;
A cycloalkyl group, an aryl group and the like. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group and an arylthio group. Further, an arylalkoxyalkyl group or the like which is a group obtained by combining these substituents, or an arylsulfonylaryl group or the like obtained by combining these substituents by bonding with an oxygen atom, a nitrogen atom, a sulfur atom, or the like is used as a substituent. Etc.

In the formula (1), the divalent or higher valent organic group X is a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above organic group. means. For example, those derived from an alkylene group, a (substituted) phenylene group, and bisphenols which are polynuclear phenols. Preferred are bisphenol A, hydroquinone, resorcinol, diphenylmethane, dihydroxydiphenyl, dihydroxynaphthalene and the like.

The phosphate compound may be a monomer, dimer, oligomer, polymer or a mixture thereof. Specifically, trimethyl phosphate,
Triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (2-ethylhexyl) phosphate, diisopropylphenyl phosphate, trixylenyl phosphate, Tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, cresyl diphenyl phosphate, or a substituted or condensed product thereof No.

The commercially available halogen-free phosphoric acid ester compounds include, for example, TPP [triphenyl phosphate], TXP [trixylenyl phosphate], CR-733S [resorcinol bis] manufactured by Daihachi Chemical Industry Co., Ltd. (Diphenyl phosphate)], CR74
1 [phenol A bis (diphenyl phosphate)],
PX200 [1,3-phenylene-teslakis (2,6
-Dimethylphenyl) phosphate, PX201
[1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphate, PX202 [4,4′-biphenylene-teslakis) 2,6-dimethylphenyl)
Phosphate esters and the like can be mentioned.

As the organic alkali metal salt and the organic alkaline earth, there are various types, and examples thereof include an alkali metal salt and an alkaline earth metal salt of an organic acid or an organic acid ester having at least one carbon atom. Here, the organic acid or organic acid ester is an organic sulfonic acid, an organic carboxylic acid, or the like. On the other hand, alkali metals are sodium, potassium,
Lithium, cesium and the like, and alkaline earth metals are magnesium, calcium, strontium, barium and the like. Among them, salts of sodium, potassium and cesium are preferably used. The salt of the organic acid is fluorine,
Halogen such as chlorine and bromine may be substituted.

Among the above various organic alkali metal salts and alkaline earth metal salts, for example, in the case of organic sulfonic acid,
Formula (2) _{(C n F 2n + 1 SO} 3) m M (2) ( wherein, n represents an integer of 1 to 10, M is lithium, sodium, potassium, an alkali metal such as cesium, or magnesium , Calcium, strontium, barium and the like, and m represents the valency of M.) An alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid represented by the following formula (1) is preferably used. Examples of these compounds include, for example, JP-B-47-4
The one described in Japanese Patent No. 0445 corresponds to this.

In the general formula (2), examples of the perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, and perfluoromethylbutanesulfonic acid. Acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid and the like. In particular, these potassium salts are preferably used. Other organic sulfonic acids such as 2,5-dichlorobenzenesulfonic acid; 2,4,5-trichlorobenzenesulfonic acid; diphenylsulfone-3-sulfonic acid; diphenylsulfone-3,3′-disulfonic acid; and naphthalenetrisulfonic acid. And alkali earth metal salts and the like. Further, a thermoplastic resin in which a sulfonic acid group, a borate group, a phosphate group, or the like is substituted for an aromatic ring of a vinyl-based thermoplastic resin can also be used. Examples of the aromatic vinyl resin include thermoplastic resins having at least a styrene structure, such as polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, and ABS resin. Among them, polystyrene resin is preferably used. Examples of the acid base include alkali metal salts and alkaline earth salts.

Examples of the organic carboxylic acid include perfluoroformic acid, perfluoromethane carboxylic acid, perfluoroethane carboxylic acid, perfluoropropane carboxylic acid, perfluorobutane carboxylic acid, perfluoromethyl butane carboxylic acid and perfluoro Examples thereof include hexane carboxylic acid, perfluoroheptane carboxylic acid, and perfluorooctane carboxylic acid, and alkali metal salts and alkaline earth metal salts of these organic carboxylic acids are used. Alkali metals and alkaline earth metals are the same as described above.

As the silicone flame retardant, there are silicone oil, silicone resin and the like. Examples of the silicone flame retardant include a silicone compound having a specific structure containing a reactive group such as an alkoxy group and an epoxy group, and a silicone resin having a specific molecular weight in which the amount of oxygen in a repeating unit is different (Japanese Patent Laid-Open No. 6-306265). Gazette, JP-A-6-33647
JP-A-8-176425, JP-A-10-176425
139964 and the like). Here, there are various compounds as the silicone-based flame retardant. Among them, a functional group-containing silicone compound, for example, a functional group-containing (poly)
Organosiloxanes whose skeleton has the formula R
⁵ _a R ⁶ _b SiO _{(4-ab) / 2} [R ⁵ is a functional group-containing group, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, 0 <a ≦ 3, 0 ≦ b <3,
0 <a + b ≦ 3], a polymer having a basic structure represented by the following formula:
It is a copolymer. Further, as the functional group, an alkoxy group,
It contains an aryloxy, polyoxyalkylene group, hydrogen group, hydroxyl group, carboxyl group, cyanol group, amino group, mercapto group, epoxy group and the like.

As these functional groups, a silicone compound having a plurality of functional groups and a silicone compound having different functional groups can be used in combination. Silicone compound having a functional group, the functional group (R ⁵⁾ / hydrocarbon group (R ⁶⁾ is usually 0.1 to 3, preferably of about 0.3 to 2. These silicone compounds are liquids, powders and the like, but those having good dispersibility in melt kneading are preferred. For example, the viscosity at room temperature is 10-500,
000 cst (centistokes) liquid. When the silicone compound has a functional group, it is characterized in that even when the silicone compound is in a liquid form, it is uniformly dispersed in the composition and bleeds less during molding or on the surface of the molded article.

The flame retardant (C) may be used alone.
Further, two or more kinds may be used in combination. The content of the resin (A) and the resin (B) 100
The amount is 0.05 to 30 parts by mass, preferably 0.1 to 20 parts by mass with respect to parts by mass. If the content is too small, it is difficult to achieve the target flame retardancy, and if it is too large, the effect of improving the flame retardancy corresponding to the amount is not recognized,
Rather, it is economically disadvantageous. As the flame retardant (C), phosphorus-based flame retardants, organic alkali metal salts, organic alkaline earth metal salts, and silicone-based flame retardants are particularly preferred.

(D) The fluororesin is added for the purpose of preventing the molten resin from dripping during combustion. As the fluorine-based resin, usually a polymer containing a fluoroethylene structure, a copolymer,
For example, a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a copolymer of tetrafluoroethylene and a fluorine-free ethylene-based monomer can be given. Preferably, polytetrafluoroethylene (PT
FE), whose average molecular weight is preferably at least 500,000, particularly preferably 500,000.
0 to 10,000,000. As the polytetrafluoroethylene that can be used in the present invention, all types known at present can be used.

In the polytetrafluoroethylene,
The use of a material having a fibril-forming ability can provide higher anti-dripping properties. There is no particular limitation on polytetrafluoroethylene having a fibril-forming ability, and examples thereof include those classified into Type 3 in the ASTM standard. Specific examples thereof include, for example, Teflon 6-J (manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.), Polyflon D-1, Polyflon F-103,
Polyflon F201 (manufactured by Daikin Industries, Ltd.), CD
076 (made by Asahi ICI Fluoropolymers Co., Ltd.)
And the like.

Other than those classified into the above-mentioned type 3, for example, Algoflon F5 (manufactured by Montefluos), polyflon MPA, polyflon FA-100
(Manufactured by Daikin Industries, Ltd.). These polytetrafluoroethylenes (PTFE) may be used alone or in combination of two or more. Polytetrafluoroethylene having a fibril-forming ability as described above is, for example, tetrafluoroethylene in an aqueous solvent, in the presence of sodium, potassium, ammonium peroxydisulfide, at a pressure of 1 to 100 psi, and at a temperature of 0 to 200 ° C. And preferably at 20 to 100 ° C.

Polytetrafluoroethylene having a fibril-forming ability can be obtained, for example, by adding tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium and ammonium peroxydisulfide under a pressure of 1 to 100 psi, at a temperature of 0 to 200 ° C. It is preferably obtained by polymerizing at 20 to 100 ° C.

Here, the content of the fluororesin is (A)
The amount is 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the resin comprising the component and the component (B). Here, if the amount is less than 0.05 parts by mass, the desired flame retardancy may not be sufficient to prevent the molten dripping. If the amount exceeds 2 parts by mass, the effect corresponding thereto is not improved, and The impact and the appearance of the molded product may be adversely affected. Therefore, the degree of flame retardancy required for each molded article, for example, UL-0 V-0, V-1, V-
According to 2 and the like, it can be appropriately determined in consideration of the amount of other components used and the like.

(E) As the inorganic filler, talc, mica, wollastonite, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber,
Examples thereof include carbon fiber and potassium titanate. Among them, talc, mica, and wollastonite are preferably used. These inorganic fillers are preferably in the form of plate-like fillers. Talc is a hydrated silicate of magnesium, and commercially available talc can be used. Further, as the talc used here, one having an average particle size of 0.1 to 50 μm is used, and one having an average particle size of 0.2 to 20 μm is particularly preferably used. The content of the inorganic filler is based on 100 parts by mass of the resin composed of the component (A) and the component (B).
It is 0.05 to 20 parts by mass, preferably 0.1 to 15 parts by mass. Here, if it is less than 0.05 parts by mass, the intended rigidity and flame retardancy may not be sufficiently improved,
If the amount exceeds 20 parts by weight, the effect is not improved correspondingly, and the impact resistance and the appearance of the molded product may be adversely affected.

The polycarbonate resin composition of the present invention can contain the following additive components as required. For example, phenol-based, phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (providing permanent antistatic properties), benzotriazole-based and benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers (Weathering agent), plasticizer, antibacterial agent, compatibilizer,
Coloring agents (dyes and pigments); The amounts of these components are not particularly limited as long as the characteristics of the polycarbonate resin composition of the present invention are maintained. These mixing ratios are appropriately determined in consideration of the molecular weight of the terminal-modified polycarbonate resin and the like, the type of the polyolefin-based resin, the melt flow rate, the use of the molded product, the size, the thickness, and the like.

Next, a method for producing the polycarbonate resin composition of the present invention will be described. In the polycarbonate resin composition of the present invention, the components (A), (B), (C), (D) and (E) are added at the above-mentioned ratio, and the above-mentioned additional components used as necessary are further added at a predetermined ratio. It is obtained by blending and kneading. The compounding and kneading at this time are usually used equipment, for example, premixed with a ribbon blender, a drum tumbler or the like, and a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extruder and It can be performed by a method using a coneder or the like. The heating temperature during kneading is appropriately selected usually in the range of 240 to 300 ° C. As the melt-kneading molding, it is preferable to use an extruder, particularly a vent-type extruder. The components other than the polycarbonate resin can be added as a master batch.

The polycarbonate resin composition of the present invention comprises:
A molded product is directly manufactured using the above-described melt-kneading molding machine, or the obtained pellet is used as a raw material, and is used as an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method. Various molded products can be manufactured by a method and a foam molding method. However, a pellet-shaped molding raw material is produced by the above-mentioned melt-kneading method, and then the pellets can be used particularly suitably for production of an injection-molded article by injection molding or injection compression molding. In addition, as an injection molding method, gas injection molding for preventing sink marks on the appearance or reducing the weight can also be adopted.

Molded articles obtained from the polycarbonate resin composition of the present invention include electric machines such as copiers, faxes, televisions, radios, tape recorders, video decks, personal computers, printers, telephones, information terminals, refrigerators, microwave ovens and the like. -Used in housings or parts of electronic equipment, and also in other fields such as automobile parts.

[0052]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Production Example 1 A mixture of 1-eicosene, 1-docosene and 1-tetracosene [composition ratio (mol%); 53.3: 40.2: 6.5] was placed in a 260 liter reaction vessel equipped with a stirrer for synthesis of monoalkylphenol (AP2024). 3 kg of 57 ten, 70 kg of phenol and 7 kg of galeonite # 136 as a catalyst (manufactured by Mizusawa Chemical Industry Co., Ltd.)
The reaction raw material and the catalyst were charged and reacted at 145 ° C. for 80 minutes with stirring in a nitrogen stream. After the reaction,
After the catalyst was filtered off, it was separated from heavy components such as phenol and dialkylphenol by vacuum distillation to purify monoalkylphenol (AP2024). As a result of analyzing the purified AP2024 by gas chromatography, it contained 500 ppm of phenol and no dialkylphenol peak was detected. The composition ratio (%) of the ortho, para and meta isomers of the obtained AP2024 was 50: 48: 2 (mol%), and the APHA
Was 10. The average carbon number of the alkyl group of AP2024 was 21.

2. Preparation of terminal AP2024-modified polycarbonate resin Synthesis of polycarbonate oligomer Bisphenol A was dissolved in a 5.6% by mass aqueous sodium hydroxide solution so that bisphenol A concentration became 13.5% by mass to prepare a sodium hydroxide aqueous solution of bisphenol A. did. Phosgene was continuously supplied at a flow rate of 40 liters / hr of an aqueous sodium hydroxide solution of bisphenol A and 15 liters / hr of methylene chloride to a tubular reactor having an inner diameter of 6 mm and a length of 30 m at a flow rate of 4.0 kg / hr. The tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket. The reaction solution exiting the tubular reactor was continuously introduced into a baffled tank reactor having an inner volume of 40 liters equipped with a swept wing, and further, 2.8 liters of an aqueous sodium hydroxide solution of bisphenol A was added thereto. hr, 25% by mass aqueous sodium hydroxide solution 0.07 L / hr, water 17 L / hr, and 1% by mass triethylamine aqueous solution 0.64
The reaction was carried out by supplying 2.15 l / hr of a 10.3 mass methylene chloride solution of the AP2024 described above. The reaction solution overflowing from the tank reactor was continuously withdrawn, and the aqueous phase was separated and removed by standing, and the methylene chloride phase was collected. The concentration of the polycarbonate oligomer thus obtained was 323 g / l, and the concentration of the chloroformate group was 0.69 mol / l.

The oligomer solution 10 was placed in a 50-liter tank reactor equipped with a synthetic baffle of polycarbonate, two paddle-type stirring blades, and a cooling jacket.
Liter, methylene chloride 6.15 liter, AP2
024158 g and 3.84 ml of triethylamine were charged, and sodium 226 dithionite was added thereto.
mg of a 6.4 mass% aqueous sodium hydroxide solution (1,720 g) was added thereto with stirring, and the reaction was carried out for 20 minutes. In this reaction step, the reaction was controlled by cooling so that the reaction temperature did not become 20 ° C. or higher. Next, an aqueous sodium hydroxide solution of bisphenol A (a solution in which 331 g of NaOH and 1.32 g of sodium dithionite are dissolved in 4.8 g of water and 660 g of bisphenol A) is added, and the mixture is stirred at 300 rpm for 40 minutes. A polymerization reaction was performed.

Washing Step: To dilute, 10 liters of methylene chloride was added, and the mixture was stirred and allowed to stand for 20 minutes to separate an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and sodium hydroxide. It was extracted from the lower part of the vessel and isolated. A solution of the polycarbonate thus obtained in methylene chloride was successively added to 15% by volume of 0.03
Washed with an aqueous solution of sodium hydroxide (mol / liter), hydrochloric acid (0.2 mol / liter) and then twice with pure water,
It was confirmed that the electric conductivity in the aqueous phase after washing was 0.01 μS / m or less.

Flaking Step A methylene chloride solution of polycarbonate obtained by washing is concentrated and pulverized, and the obtained flakes are reduced to 100 ° C. under reduced pressure.
And dried.

Production Example 2 1. Production of Polycarbonate Resin Modified with p-Dodecylphenoxy Terminal (PDDP) Group Synthesis of Polycarbonate Oligomer In 400 liters of a 5% by mass aqueous sodium hydroxide solution,
60 kg of bisphenol A was dissolved to prepare an aqueous sodium hydroxide solution of bisphenol A. Then, the sodium hydroxide aqueous solution of bisphenol A kept at room temperature was passed through an orifice plate at a flow rate of 138 liters / hour and methylene chloride at a flow rate of 69 liters / hour through a tubular reactor having an inner diameter of 10 mm and a length of 10 m. Introduce,
Phosgene was blown into the mixture at a flow rate of 10.7 kg / hour and reacted continuously for 3 hours. The tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was kept at 25 ° C. by passing cooling water through the jacket portion. or,
The pH of the discharged liquid was adjusted to be 10 to 11. The reaction solution thus obtained was allowed to stand, whereby the aqueous phase was separated and removed, and the methylene chloride phase (220 liters) was collected to obtain a polycarbonate resin oligomer (concentration: 3).
17 g / l). The degree of polymerization of the polycarbonate resin oligomer obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7 normal.

Synthesis of Polycarbonate 10 liters of the above oligomer solution was placed in a container with stirring of 50 liter inner volume, and p-dodecylphenol (P
162 g of (DDP) (containing a branched dodecyl group) [manufactured by Yuka Schenectady] was dissolved. Next, an aqueous solution of sodium hydroxide (53 g of sodium hydroxide, 1 liter of water)
And 5.8 cc of triethylamine, and add
The mixture was stirred at rpm and reacted. Thereafter, a sodium hydroxide solution of bisphenol A (720 g of bisphenol A, 412 g of sodium hydroxide, 5.5 liter of water) was mixed with the above system, and 8 liter of methylene chloride was added.
The reaction was stirred at 500 rpm for a time. After the reaction, 7 liters of methylene chloride and 5 liters of water were added, and the mixture was stirred for 10 minutes at 500 rpm. After the stirring was stopped, the mixture was allowed to stand, and the organic phase and the aqueous phase were separated. The obtained organic phase was washed with 5 liters of alkali (0.03 N-NaOH), 5 liters of acid (0.2 N-hydrochloric acid) and 5 liters of water (twice). Thereafter, the methylene chloride was evaporated to obtain a flaky polymer. The viscosity average molecular weight is 17,500
Met.

Examples 1 to 5 and Comparative Examples 1 to 8 Each component was blended in the proportions shown in Tables 1 and 2 [Components (A) and (B) were mass%, and the other components were (A ) And 100 parts by mass of the resin composed of the component (B). ] And a vent-type twin-screw extruder (model: TEM
35, manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at 280 ° C., and pelletized. In all Examples and Comparative Examples, Irganox 107 was used as an antioxidant.
6 (manufactured by Ciba Specialty Chemicals) and 0.1 part by mass of ADK STAB C (manufactured by Asahi Denka Kogyo Co., Ltd.). The obtained pellet is heated at 120 ° C.
After drying for 12 hours at a molding temperature of 270 ° C. and a mold temperature of 8
A test piece was obtained by injection molding at 0 ° C. The performance was evaluated by the following various tests using the obtained test pieces, and the results are shown in Tables 1 and 2.

The molding materials used and the method for evaluating the performance are described below. (A) Polycarbonate resin PC-1: terminal AP2024 obtained in Production Example 1 above
Modified polycarbonate resin PC-2: p-dodecylphenoxy (PDDP) group-modified polycarbonate resin PC-3 obtained in Production Example 2 above: Tafflon A1900 (manufactured by Idemitsu Petrochemical Co., Ltd.): bisphenol A polycarbonate resin, MF
R = 19 g / 10 min (temperature: 300 ° C., load: 11.7)
7N), viscosity average molecular weight: 19,000, terminal p-te
rt-butylphenoxy group-modified polycarbonate resin

(B) Polyolefin resin PP: homopolypropylene, Idemitsu J-700M (manufactured by Idemitsu Petrochemical Co., Ltd.) PE: low density polyethylene, Tosoh 291A (manufactured by Tosoh Corporation) (C) Flame retardant FR-1: polystyrene Sodium sulfonate (manufactured by Lion) FR-2: Bisphenol A bis (diphenyl phosphate), CR741 (manufactured by Daihachi Chemical) FR-3: TBA oligomer, FG7500, FR-4 manufactured by Teijin Chemicals: Contains vinyl group methoxy group Methylphenyl silicone, KR219, manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity = 18
mm ² / s (D) Fluorine-based resin PTFE: F201L, manufactured by Daicel Chemical Industries, Ltd. (E) Inorganic filler talc: TPA25, manufactured by Fuji Talc

[Performance Evaluation Method] (1) IZOD (Izod Impact Strength) According to ASTM D256, 23 ° C. (wall thickness: 3.2 m)
m), unit: kJ / m ² (2) Weld strength Tensile strength test specimens were molded with a two-point gate using a die, and the tensile strength was measured. (3) Friction coefficient Sliding characteristics A contact surface between a disk and a cylinder when a plate-shaped test piece is rotated under a load of 2 kg in accordance with the method A of JIS K7218 (test method for sliding abrasion of plastic). The average value (kg) of the maximum frictional force generated over 5 minutes was measured. The coefficient of friction was evaluated as friction coefficient (kg) / load 2 kg. (4) Q value (flow value) Measured at a load of 160 kg and a temperature of 280 ° C. in accordance with JIS K7210. (5) Grease resistance The grease resistance was based on the chemical resistance evaluation method (critical distortion due to 1/4 ellipse). A sample piece (thickness: 3 mm) was fixed to a jig (1/4 elliptical surface) shown in FIG. 1 (perspective view), and Albanian grease (manufactured by Showa Shell Sekiyu KK) was applied to the sample piece and held for 48 hours. . The minimum length (X) at which cracks occurred was read, and the critical strain (%) was determined from the following equation. Critical strain (%) = (b / 2a ² ) [1- [1 / a ² − (b ²
/ A ⁴ )] X ² ] ⁻³ / ² · ^t (t: test piece thickness) (6) Flame retardant UL94 combustion test (test piece thickness: 1.5 mm) NG is V-0 , V-1, and V-2. (7) The cut surface of the surface layer peeled / appeared molded product was visually observed. 〇: good without surface layer peeling, □: slight surface layer peeling, ×: surface layer peeling

[0063]

[Table 1]

[0064]

[Table 2]

From the results in Table 1, it can be seen that the molded article made of the polycarbonate resin composition of the present invention has high flame retardancy, and is excellent in solvent resistance, slidability and melt fluidity. By using the terminal alkylphenoxy-modified polycarbonate resin, compatibility is improved, delamination is prevented, and impact strength and weld strength are also improved. Also, from the results in Table 2, the flame retardancy was poor and the solvent resistance and slidability were insufficient.

[0066]

According to the present invention, a flame-retardant polycarbonate resin composition having good compatibility, free from laminar peeling and poor appearance, and excellent in solvent resistance and sliding properties, and a molded article of the resin composition are provided. Obtainable.

[Brief description of the drawings]

FIG. 1 is a perspective view of a test piece mounting jig for evaluating the grease resistance of the composition of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 27:18) F-term (Reference) 4F071 AA14 AA15 AA20 AA22 AA27 AA50 AA67 AA79 AB03 AB18 AB20 AB21 AB24 AB28 AB30 AC06 AC11 AC12 AC14 AC15 AD01 AE07 AE17 AH07 AH12 BA01 BB05 BC03 4J002 BB032 BB052 BB122 BB142 BB152 BB172 BB243 BC113 BD124 BD154 CD123 CG001 CG033 CP033 DA017 DE076 DE146 DE187 DE237 DG047 DG0EG EG077 DJ0077 DJ007 DJ037 DJ0070 GQ00

Claims (8)

[Claims] 1. A resin comprising (A) 60 to 97% by mass of a polycarbonate resin capped with a phenoxy group having an alkyl group having 10 to 35 carbon atoms and (B) 3 to 40% by mass of a polyolefin resin. With respect to 100 parts by mass, (C) 0.05 to 30 parts by mass of a flame retardant, (D) 0 to 2 parts by mass of a fluororesin, and (E) 0 to 20 parts of an inorganic filler.
A polycarbonate resin composition containing parts by mass. 2. The polycarbonate resin composition according to claim 1, wherein the polyolefin resin is at least one resin selected from a polyethylene resin and a polypropylene resin. 3. The polycarbonate resin composition according to claim 1, wherein the flame retardant is one or more flame retardants selected from phosphorus-based flame retardants, organic alkali metal salts, organic alkaline earth metal salts, and silicone-based flame retardants. . 4. The polycarbonate resin composition according to claim 1, wherein the fluororesin is polytetrafluoroethylene having a fibril-forming ability. 5. The polycarbonate resin composition according to claim 1, wherein the inorganic filler is a plate-like filler. 6. The polycarbonate resin composition according to claim 5, wherein the platy filler is at least one platy filler selected from talc, mica and wollastonite. 7. A molded article comprising the polycarbonate resin composition according to claim 1. 8. A housing or component of an electric / electronic device comprising the polycarbonate resin composition according to claim 1.